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二肽-铜杂化纳米颗粒作为用于测定和降解酚类污染物及肾上腺素的高效漆酶模拟物

Dipeptide-Copper Hybrid Nanoparticles as Efficient Laccase Mimics for Determination and Degradation of Phenolic Pollutants and Epinephrine.

作者信息

Feng Lisha, Mao Kejing, Zhu Xinyu, Chen Yuyuan, Ye Jianbin, Zheng Yongfang, Zhu Hu

机构信息

Fujian-Taiwan Science and Technology Cooperation Base of Biomedical Materials and Tissue Engineering, Engineering Research Center of Industrial Biocatalysis, Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, 32 Shangsan Road, Fuzhou 350007, China.

Key Laboratory of Translational Tumor Medicine in Fujian Province, Putian University, Putian 351100, China.

出版信息

ACS Omega. 2025 Apr 14;10(15):15553-15562. doi: 10.1021/acsomega.5c00623. eCollection 2025 Apr 22.

Abstract

The broad application of laccase mimics is notably constrained by their costly and intricate synthesis routes. For example, researchers often use peptides to coordinate with copper ions to mimic the active sites of laccases, thereby constructing laccase mimics. However, these synthetic methods are quite complex, such as requiring high temperatures, the use of organic solvents, long durations, and cumbersome procedures. In this study, we introduce a straightforward yet highly active, robust, and versatile laccase mimic known as HH-Cu, which was synthesized through a simple precipitation reaction by combining the dipeptide HH with Cu ions in phosphate-buffered saline (PBS). By adjusting the ratio of HH to copper ions, we were able to produce the most effective organic-inorganic hybrid nanoparticles, namely, HH-Cu, which outperforms the HH-Cu nanoflowers. HH-Cu demonstrates extraordinary catalytic efficiency, with a 4.7-fold higher maximum velocity ( ) and a lower Michaelis constant ( ) compared to natural laccase. This nanozyme is also remarkably resilient under harsh conditions such as extreme pH levels, high temperatures, and high salinity, and it shows excellent storage stability and reusability. We successfully applied this nanozyme for the degradation and quantitative detection of various phenolic pollutants and epinephrine. HH-Cu demonstrates a markedly superior sensitivity for detecting epinephrine than laccase and offers a comparable limit of detection and a broader linear range compared to other laccase mimics. This research should lay the groundwork for ongoing efforts in the development of organic-inorganic hybrid nanozymes and provide an effective method for the simple and efficient synthesis of laccase mimics.

摘要

漆酶模拟物的广泛应用受到其昂贵且复杂的合成路线的显著限制。例如,研究人员经常使用肽与铜离子配位以模拟漆酶的活性位点,从而构建漆酶模拟物。然而,这些合成方法相当复杂,比如需要高温、使用有机溶剂、耗时较长且程序繁琐。在本研究中,我们引入了一种简单直接但活性高、稳定性强且用途广泛的漆酶模拟物,称为HH-Cu,它是通过在磷酸盐缓冲盐水(PBS)中将二肽HH与铜离子结合,经简单沉淀反应合成的。通过调整HH与铜离子的比例,我们能够制备出最有效的有机-无机杂化纳米颗粒,即HH-Cu,其性能优于HH-Cu纳米花。HH-Cu表现出非凡的催化效率,与天然漆酶相比,其最大反应速度( )高出4.7倍,米氏常数( )更低。这种纳米酶在极端pH值、高温和高盐度等恶劣条件下也具有显著的稳定性,并且具有出色的储存稳定性和可重复使用性。我们成功地将这种纳米酶应用于各种酚类污染物和肾上腺素的降解及定量检测。与漆酶相比,HH-Cu在检测肾上腺素方面表现出明显更高的灵敏度,与其他漆酶模拟物相比,其检测限相当,线性范围更宽。本研究应为有机-无机杂化纳米酶的持续开发奠定基础,并为简单高效地合成漆酶模拟物提供一种有效方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9e4c/12019501/7135dcf4fdcf/ao5c00623_0006.jpg

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